This invention relates to a functional polymer comprising active and stable functional groups, and to a method of preparing the same. More particularly, the present invention relates to a functional polymer bearing nonmetal oxyacid derivatives on dimethylene spacers, comprising repeat units that are of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94X(O)mR1nR2]xe2x80x94CH2xe2x80x94 wherein X(O)mR1nR2 is a nonmetal oxyacid derivative, and to methods of its preparation.
Functional polymers are widely used in industry as separation media and as solid-phase reagents, catalysts and protecting groups for analytical or preparative chemical applications and processes [D. C. Sherrington and P. Hodge, xe2x80x9cSyntheses and Separations Using Functional Polymersxe2x80x9d, John Wiley and Sons, Toronto, 1988]. A functional polymer generally consists of a polymer matrix, in the form of particles, beads or a porous block [C. Viklund, F. Svek, J. M. J. Frxc3xa9chet and K. Irgum, xe2x80x9cMolded porous materials with high flow characteristics for separation or catalysis: control of porous properties during polymerization in bulk solutionxe2x80x9d, Chem. Mater. y1986 v8 p744-750], that is chemically inert to the conditions of its use, including being insoluble in any solvent it is likely to encounter so that it can be retained in a column or easily recovered from out of a product mixture by filtration or other separation for easy isolation of chemical product and reuse of the functional polymer; and also of functional groups, attached to the polymer matrix, that can bind, transform or otherwise interact with chemical species that are dissolved in a permeating fluid, or that confer other advantageous properties to the functional polymer, such as a higher density for best use in floating bed reactors or for easier and faster separation by precipitation, or better wetting and penetration by a particular solvent. Most often, the polymer matrix is of crosslinked polystyrene, due to the ease of its preparation through suspension or other polymerization of styrene or styrene-like monomer (usually, including divinylbenzene as crosslinking agent), with attendant control of particle size, porosity, swellability, surface area, and other aspects of its architecture affecting eventual use; and its good general mechanical and chemical stabilities, though also with the ability to be controllably decorated with any of a wide variety of functional groups. In ion exchange resins, which are manufactured in large quantities for deionizing water and many other purification processes, these functional groups may consist of sulfonic, carboxylic, phosphinic or phosphonic acids or phosphonic ester acids or their salts, or amines or their salts, or quaternary ammonium or phosphonium hydroxides or other of their salts; recoverable solid resins for general acid catalysis would bear sulfonic or phosphoric strong acid groups; chelating resins that recover toxic or expensive metal ions from wastewater may contain combinations of amino and sulfonate, phosphinate, phosphonate [S. D. Alexandratos, and D. R. Quillen, Reactive Polym. y1990 v12 p255-265] or carboxylate groups, along with hydroxyl, ether, thiol, sulfide, phosphine, phosphoramidate or other Lewis base groups; certain of these groups may also coordinate with metal ions to activate their negative counterions for phase-transfer catalyzed nucleophilic substitution or other reactions, or may hold platinum or other catalytic heavy metal species so that these are conserved and re-used from one reaction to the next; halosilyl, haloalkyl, haloacyl, halophosphinyl, halophosphonyl or halosulfonyl functional groups, or anhydride or azlactone functional groups, can covalently bind to other organic molecules so that parts of these are protected while other parts are being chemically modified, the whole later released, such as in solid-phase synthesis of polypeptides, polysaccharides or polynucleotides or themselves act as agents for catalysis or molecular recognition, as with proteinic enzymes, antibodies or antigens that have been polymer-bound. Phosphorus-containing functional groups can improve fire resistance sorption in a functional polymer.
While functional polymers may be prepared by polymerization of monomers that already contain the desired functional groups, more commonly they are made by chemically functionalizing or modifying other existing polymer matricesxe2x80x94most commonly, crosslinked polystyrenexe2x80x94as prepared from common monomers through established polymerization recipes that give well-defined and desirable particle and matrix structures and properties. However, existing such modification methods of preparing functional polymers often suffer from disadvantages of hazardous or expensive ingredients or conditions, that result in products that are intrinsically deficient in activity or stability or both [G. D. Darling and J. M. J. Frxc3xa9chet xe2x80x9cDimethylene spacers in functionalized polystyrenesxe2x80x9d, in J. L. Benham and J. F. Kinstle, Eds. xe2x80x9cChemical Reactions on Polymersxe2x80x9d, ACS Symp. Ser. v364, American Chemical Society, Washington D.C., y1988 p24-36]. For example, the chloromethylation route to the most common anion-exchange and chelating polystyrene-based resins uses or generates highly carcinogenic species, and results in benzyl-heteroatom bonds that are unstable to many conditions of eventual use or regeneration; bromination/lithiation, another general route to functional polymers, employs expensive and sensitive organometallic reagents and, like sulfonation, results in aryl-heteroatom functional groups that may be unstable in acidic conditions. Functional polymers containing aliphatic spacer groups of at least two carbons between polystyrene phenyl and functional group heteroatom would not show either type of chemical instability, and moreover, the deeper penetration of the dangling functional groups into a fluid phase permeating the polymer matrix often allows better and faster interactions with soluble species therein [A. Deratani, G. D. Darling, D. Horak and J. M. J. Frxc3xa9chet xe2x80x9cHeterocyclic polymers as catalysts in organic synthesis. Effect of macromolecular design and microenvironment on the catalytic activity of polymer-supported (dialkylamino)pyridine catalysts.xe2x80x9d Macromolecules y1987 v20 p767]. Several such spacer-containing functional polymers have been prepared via electrophilic aromatic substitutionxe2x80x94either chloromethylation or bromination/lithiationxe2x80x94of aryl nuclei in crosslinked styrene-divinylbenzene copolymer, albeit through tedious multistep syntheses [Darling and Frxc3xa9chet y1988 ibid].
Instead of on styrenic phenyl, modification reactions can be performed on the vinyl groups of polymeric 1-(vinylphenyl)ethylene repeat units. These vinyl groups may be prepared from formyl, chloromethyl, bromoethyl or 1,2-dibromoethyl functional group precursors [M. J. Farrell, M. Alexis and M. Trecarten, Polymer y1983 v24 p114; Darling and Frxc3xa9chet y1988 ibid; T. Yamamizu, M. Akiyama and K. Takeda, React. Polym. y1985 v3 p173], or remain from anionic [Y. Nagasaki, H. Ito, T. Tsuruta, Makromol. Chem. y1968 v187 p23] or even free-radical [M. C. Faber, H. J. van den Berg, G. Challa and U. K. Pandit, React. Polym. y1989 v11 p117] copolymerization of monomer mixtures that include divinylbenzene. Radial copolymerization with divinylbenzene is a particularly simple way to form a polymer that contains such vinyls, that moreover have here the advantage of being site-isolated; indeed, Rohm and Haas supplies a commercial product, xe2x80x9cAmberlite(copyright) XAD-4 nonionic polymeric adsorbentxe2x80x9d, which analysis thereof indicates to be undoubtedly made by radical copolymerization of a mixture of divinylbenzene and ethylstyrenexe2x80x94which mixture, containing both meta and para isomers of each, is commercially provided under the name xe2x80x9ctechnical-grade divinylbenzenexe2x80x9d [xe2x80x9cAldrich Catalogxe2x80x9d y1997], and so which resulting polymer may be called xe2x80x9cpoly(divinylbenzene)xe2x80x9dxe2x80x94and which contains 30 mol % of polymeric 1-(vinylphenyl)ethylene repeat units, with the remaining repeat units consisting of polymeric 1-(ethylphenyl)ethylene and crosslinking polymeric bis(ethylene)phenyl repeat units [Faber et al y1989 ibid]. Through electrophilic, nucleophilic, radical, transition-metal catalyzed or other additions to such polymeric 1-(vinylphenyl)ethylene repeat units. [W. Obrecht, Y. Seitz and W. Funke, Makromol. Chem. y1976 v177 p2235; Faber et al y1989 ibid; Z. Zhengpu, P. Hodge and P. W. Stratford, React. Polym. y1991 v15 p71; J. P. Gao, F. G. Morin and G. D. Darling, Macromolecules y1993 v26 p1196], or by their radical-induced graft copolymerizations with various monomers [T. Brunelet, M. Bartholin and A. Guyot, Angew. Makromol. Chem. y1982 v106 p79], have been provided a wide variety of functional groups, including of the form Psxe2x80x94CH2xe2x80x94CH2xe2x80x94X, wherein Ps represents a crosslinked polystyrene matrix connecting through phenyl, and X a functional group connecting through a heteroatom, that features advantageous dimethylene spacer [Gao et al y1993 ibid].
Useful functional groups that are derivatives of nonmetal oxyacids such as sulfonate or phosphonate may be incorporated into functional polymers through polymerizations with such comonomers as vinylsulfonate, vinylphosphonate, vinylphenylsulfonate or vinylphenylphosphonate. As previously mentionned though modification of an existing optimal polymer matrix is a route often to be preferred for its simplicity, versatility, economy and better product properties. Though aryl sulfonation of crosslinked polystyrene and its product Psxe2x80x94SO3H are well known, and nucleophilic substitution of Psxe2x80x94CH2xe2x80x94Cl has provided Psxe2x80x94CH2xe2x80x94SO3xe2x88x92, Psxe2x80x94CH2xe2x80x94PO(OCH3)2 and other polymer-supported nonmetal oxyacid derivatives of general form Psxe2x80x94CH2xe2x80x94X, as well as Psxe2x80x94CH2xe2x80x94CH(PO(OCH3))2 via similar nucleophilic substitution by methylene bis(dimethylphosphonate) anion onto Psxe2x80x94CH2xe2x80x94Cl, the prior art does not contain a functional polymer bearing acid, salt, ester, halo or amide derivatives of nonmetal oxyacid on dimethylene spacers, of general form Psxe2x80x94CH2CH2xe2x80x94X wherein Ps represents a crosslinked polystyrene matrix connecting through phenyl, and X a nonmetal oxyacid functional group connecting through a nonmetal atom such as S or P of oxidation state  greater than 0, nor have methods been described for their preparation, including by radical additions to 1-(vinylphenyl)ethylene repeat units, oxidation of other Psxe2x80x94CH2CH2xe2x80x94X wherein X is a functional group connecting through a nonmetal atom of lower oxidation state, or by protonation, deprotonation or exchange of substituents on the connecting oxidized nonmetal atom of the forementionned nonmetal oxyacid derivative X.
It is an object of this invention to provide a functional polymer bearing nonmetal oxyacid derivatives on dimethylene spacers for separation or reactive processes in chemical manufacture or analysis.
It is another object of this invention to provide a functional polymer that can be prepared using readily-available materials and simple conditions and apparatus.
It is another object of this invention to provide a functional polymer, the architecture of whose polymer matrix (e.g. particle size and shape, porosity, swellability, surface area), and type, arrangement and number of whose functional groups, can be controlled.
It is another object of this invention to provide a functional polymer whose functional groups are stable, active, and accessible to a permeating fluid.
It is another object of this invention to provide a functional polymer bearing functional groups that are sulfonic acid, sulfonate salt, sulfonate ester, sulfonamide, sulfonyl halide, phosphonic acid, phosphonate salt, phosphonyl halide, phosphonate ester or phosphonamide, or combinations thereof, in type, arrangement and number sufficient to confer or contribute towards acidity, basicity, ion exchange, fire-resistance, wettability, chelation, extraction, separation, sorption, density, permeability, catalysis, selectivity, hydrophilicity, reactivity, seperability, suspendability, binding of ions, binding of organic molecules, binding of polypeptides, binding of polysaccharides, binding of polynucleotides, molecular recognition, filterability, convertability to other functional groups, or other desirable qualities, or combinations thereof, in a separation medium, chromatographic medium, purification medium, ion-exchange medium, chelating medium, solid-phase reagent, solid-phase catalyst, solid-phase protecting agent, support for solid-phase synthesis, chemical intermediate, or other application of a functional polymer, or combinations thereof.
In accordance with the invention there is provided a functional polymer bearing nonmetal oxyacid derivatives on dimethylene spacers, comprising repeat units of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94X(O)mR1nR2]xe2x80x94CH2xe2x80x94, wherein X is selected from nonmetals S and P, m is selected from 2 with X=S, or from 1 with X=P, R1 is selected from Cl, Br, Oxe2x88x92, OH, R3, OR3, NH2, NHR3, NR3R4 and NR5R6 with X=P, n is selected from 0 with X=S, or from 1 with X=P, R2 is selected from Cl, Br, Oxe2x88x92, OH, OR7, NH2, NHR7, NR7R8 and NR9R10, wherein R3, R4, R7 and R8 are selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-ethylhexyl, hexadecyl, 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-butoxyethyl, 2-aminoethyl, cyclohexyl, phenyl, benzyl, 4-nitrobenzyl, tolyl, a polypeptide, a polysaccharide and a polynucleotide, and R5, R6, R9 and R10 are selected from cyclic xe2x80x94(CH2)qxe2x80x94 where q is selected from 2 to 5.
In accordance with another aspect of the invention, there is provided a provided a functional polymer that can be prepared by reacting a pre-existing polymer comprising polymeric 1-(vinylphenyl)ethylene repeat units with a compound HX(O)mR1nR2 in the presence of free radicals.
In accordance with another aspect of the invention, there is provided a provided a functional polymer that can be prepared by reacting a pre-existing polymer comprising repeat units of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94X(O)mR1nR2]xe2x80x94CH2xe2x80x94 wherein X is of a lower oxidation state with oxidizing agent so as to oxidize X to a higher oxidation state.
In accordance with another aspect of the invention, there is provided a functional polymer that can be prepared by reacting a pre-existing polymer comprising repeat units of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94X(O)mR1nR2]xe2x80x94CH2xe2x80x94 with reagents and conditions so as to transform substituent R1 to a different substituent R11 or substituent R2 to a different R12 or both.
In accordance with a preferred embodiment of the invention there is provided a method of preparing a functional polymer bearing nonmetal oxyacid derivatives on dimethylene spacers, by treating a polymer that comprises polymeric 1-(vinylphenyl)ethylene repeat units with a compound HX(O)mR1nR2 dissolved in a fluid that permeates said polymer, in the presence of other compounds and under such conditions that radicals are generated in the medium, and the HX(O)mR1nR2 undergoes radical-induced addition to the 1-(vinylphenyl)ethylene repeat units.
In accordance with a preferred embodiment of the invention there is provided a functional polymer bearing nonmetal oxyacid derivatives on dimethylene spacers that has been prepared by treating polymeric 1-(vinylphenyl)ethylene repeat units with a compound HX(O)mR1nR2 in the presence of free radicals.
In accordance with a preferred embodiment of the invention there is provided a method of preparing a functional polymer bearing nonmetal oxyacid derivatives on dimethylene spacers, by treating a pre-existing polymer comprising repeat units of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94X(O)mR1nR2]xe2x80x94CH2xe2x80x94 wherein X is of a lower oxidation state with peracetic acid or other oxidizing agent dissolved in a fluid that permeates said polymer, under such conditions so as to oxidize X to a higher oxidation state.
In accordance with a preferred embodiment of the invention there is provided a functional polymer bearing nonmetal oxyacid derivatives on dimethylene spacers that has been prepared by treating a pre-existing polymer comprising repeat units of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94X(O)mR1nR2]xe2x80x94CH2xe2x80x94 wherein X is of a lower oxidation state oxidizing agent so as to oxidize X to a higher oxidation state.
In accordance with a preferred embodiment of the invention there is provided a method of preparing a functional polymer bearing nonmetal oxyacid derivatives on dimethylene spacers, by treating a pre-existing polymer comprising repeat units of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94X(O)mR1nR2]xe2x80x94CH2xe2x80x94 with reagents dissolved in a fluid permeating said polymer, under such conditions as to transform substituent R1 to a different substituent R11 or substituent R2 to a different substituent R12 or both.
In accordance with a preferred embodiment of the invention there is provided a functional polymer bearing nonmetal oxyacid derivatives on dimethylene spacers that has been prepared by treating a pre-existing polymer comprising repeat units of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94X(O)mR1nR2]xe2x80x94CH2xe2x80x94 with reagents and under conditions as to transform substituent R1 to a different substituent R11 or substituent R2 to a different substituent R12 or both.
In accordance with a preferred embodiment of the invention there is provided a functional polymer bearing nonmetal oxyacid derivatives on dimethylene spacers comprising repeat units of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94SO2R2]xe2x80x94CH2xe2x80x94 wherein R2 is selected from OH and Oxe2x88x92.
In accordance with a preferred embodiment of the invention there is provided a method of preparing a functional polymer comprising repeat units of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94SO2Oxe2x88x92]xe2x80x94CH2xe2x80x94, by reacting a pre-existing polymer comprising polymeric 1-(vinylphenyl)ethylene repeat units with HSO3xe2x88x92 in the presence of free radicals.
In accordance with a preferred embodiment of the invention there is provided a method of preparing a functional polymer comprising repeat units of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94SO2OH]xe2x80x94CH2xe2x80x94, by reacting a pre-existing polymer comprising polymeric repeat units of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94SCOCH3]xe2x80x94CH2xe2x80x94 with peracetic acid in acetic acid.
In accordance with a preferred embodiment of the invention there is provided a functional polymer comprising repeat units of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94P(O)R1R2]xe2x80x94CH2xe2x80x94 wherein R1 and R2 are selected from OH, Oxe2x88x92 and OCH3.
In accordance with a preferred embodiment of the invention there is provided a method of preparing a functional polymer comprising repeat units of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94P(O)(OCH3)2]xe2x80x94CH2xe2x80x94, by reacting a pre-existing polymer comprising polymeric 1-(vinylphenyl)ethylene repeat units with dimethylphosphite in the presence of free radicals.
In accordance with a preferred embodiment of the invention there is provided a method of preparing a functional polymer comprising repeat units of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94P(O)R2]xe2x80x94CH2xe2x80x94 wherein R2 is selected from OH and OCH3, by reacting a pre-existing polymer comprising repeat units of the form xe2x80x94CH[Phxe2x80x94CH2CH2xe2x80x94P(O)(OCH3)2]xe2x80x94CH2xe2x80x94 with aqueous acid under conditions so as to replace some OCH3 by OH.
In accordance with a preferred embodiment of the invention there is provided a functional polymer bearing nonmetal oxyacid derivatives on dimethylene spacers that has been prepared from a radical copolymer polymer of monomers comprising divinylbenzene.
In accordance with a preferred embodiment of the invention there is provided a functional polymer bearing nonmetal oxyacid derivatives on dimethylene spacers that has been prepared from a radical copolymer of monomers consisiting of meta-divinylbenzene and para-divinylbenzene and meta-ethylstyrene and para-ethylstyrene.
In accordance with a preferred embodiment of the invention there is provided a functional polymer bearing nonmetal oxyacid derivatives on dimethylene spacers that also comprises other functional groups.
In accordance with a preferred embodiment of the invention there is provided a functional polymer bearing nonmetal oxyacid derivatives on dimethylene spacers, said nonmetal oxyacid derivatives being or bearing functional groups that are sulfonic acid, sulfonate salt, sulfonate ester, sulfonamide, sulfonyl halide, phosphonic acid, phosphonate salt, phosphonyl halide, phosphonate ester or phosphonamide, or combinations thereof, in type, arrangement and number sufficient to confer or contribute towards acidity, basicity, ion exchange, fire-resistance, wettability, chelation, extraction, separation, sorption, density, permeability, catalysis, selectivity, hydrophilicity, reactivity, seperability, suspendability, binding of ions, binding of organic molecules, binding of polypeptides, binding of polysaccharides, binding of polynucleotides, molecular recognition, filterability, convertability to other functional groups, or other desirable qualities, or combinations thereof, in a separation medium, chromatographic medium, purification medium, ion-exchange medium, chelating medium, solid-phase reagent, solid-phase catalyst, solid-phase protecting agent, support for solid-phase synthesis, chemical intermediate, or other application of a functional polymer, or combinations thereof.